全文获取类型
收费全文 | 5558篇 |
免费 | 223篇 |
国内免费 | 52篇 |
专业分类
化学 | 3913篇 |
晶体学 | 70篇 |
力学 | 251篇 |
综合类 | 1篇 |
数学 | 607篇 |
物理学 | 991篇 |
出版年
2024年 | 12篇 |
2023年 | 52篇 |
2022年 | 434篇 |
2021年 | 324篇 |
2020年 | 240篇 |
2019年 | 239篇 |
2018年 | 206篇 |
2017年 | 168篇 |
2016年 | 274篇 |
2015年 | 152篇 |
2014年 | 208篇 |
2013年 | 454篇 |
2012年 | 324篇 |
2011年 | 324篇 |
2010年 | 202篇 |
2009年 | 173篇 |
2008年 | 217篇 |
2007年 | 226篇 |
2006年 | 186篇 |
2005年 | 138篇 |
2004年 | 143篇 |
2003年 | 123篇 |
2002年 | 139篇 |
2001年 | 63篇 |
2000年 | 45篇 |
1999年 | 39篇 |
1998年 | 35篇 |
1997年 | 25篇 |
1996年 | 38篇 |
1995年 | 34篇 |
1994年 | 37篇 |
1993年 | 29篇 |
1992年 | 35篇 |
1991年 | 36篇 |
1990年 | 28篇 |
1989年 | 47篇 |
1988年 | 40篇 |
1987年 | 28篇 |
1986年 | 32篇 |
1985年 | 28篇 |
1984年 | 37篇 |
1983年 | 27篇 |
1982年 | 18篇 |
1981年 | 20篇 |
1980年 | 22篇 |
1979年 | 18篇 |
1978年 | 23篇 |
1977年 | 18篇 |
1976年 | 14篇 |
1973年 | 11篇 |
排序方式: 共有5833条查询结果,搜索用时 15 毫秒
241.
Arafat A Schroën K de Smet LC Sudhölter EJ Zuilhof H 《Journal of the American Chemical Society》2004,126(28):8600-8601
This communication presents the first functionalization of a hydrogen-terminated silicon-rich silicon nitride (Si3Nx) surface with a well-defined, covalently attached organic monolayer. Properties of the resulting monolayers are monitored by measurement of the static water contact angle, X-ray photoelectron spectroscopy (XPS), and infrared reflection absorption spectroscopy (IRRAS). Further functionalization was performed by reaction of Si3Nx with a trifluoroethanol ester alkene (CH2=CH-(CH2)8CO2CH2CF3) followed by basic hydrolysis to afford the corresponding carboxylic acid-terminated monolayer with hydrophilic properties. These results show that Si3Nx can be functionalized with a tailor-made organic monolayer, has highly tunable wetting properties, and displays significant potential for further functionalization. 相似文献
242.
Mohamed S. A. El‐Gaby Ahmed M. Sh El‐Sharief Ahmed A. Atalla Abu‐Bakr A. A. M. El‐Adasy 《中国化学会会志》2004,51(2):327-333
The novel cyanothioformamides 2a‐d were prepared by treatment of isothiocyanatosulfonamides 1a‐d with potassium cyanide at room temperature. Cyclocondensation of compounds 2b,c with phenyl isocyanate as electrophile furnished the corresponding imidazolidines 3a,b . The reactivity of compound 3a towards some nitrogen nucleophiles was investigated. Thus, the thiosemicarbazone 4 and imidazo[4,5‐b]quinoxaline 6 were synthesized by condensation of compound 3a with thiosemicarbazide and o‐phenylenediamine, respectively. Treatment of 3a with hydrochloric acid afforded compound 7 . Our investigation was extended to include the reactivity of cyanothioformamide 2 towards o‐aminophenol, anthranilic acid, and o‐phenylenediamine and yielded the corresponding heterocycles 9 , 11 and 13 derivatives, respectively. Structures of the synthesized compounds were established by their elemental analysis and spectral data. 相似文献
243.
The tris(2-fluoro-6-pyridylmethyl)amine ligand, F3TPA, can easily be prepared by reaction of 2-fluoro-6-bromomethylpyridine with NH4Cl in the presence of NaOH. Complexation to FeCl2 affords the high-spin F3TPAFe(II)Cl2 complex, the X-ray structure of which is reported. The three fluorine substituents provide enough steric hindrance to force the tripod to coordinate in the tridentate mode, affording a trigonal bipyramidal iron center. This complex is thermally stable, and it reacts instantaneously with molecular dioxygen to afford the unsymmetrical micro-oxo dimer F3TPAFe(III)ClOFe(III)Cl3 as the major product, together with small amounts of the mixed salt [F3TPAFe(II)Cl]2, [Fe(III)2OCl6]. These two complexes have been isolated and characterized by X-ray diffraction analysis. A mechanism by which they are obtained is suggested and seems to parallel the well-known process of autoxidation of ferrous porphyrins. 相似文献
244.
Abdelrahman AI Thickett SC Liang Y Ornatsky O Baranov V Winnik MA 《Macromolecules》2011,44(12):4801-4813
Lanthanide-encoded polystyrene particles synthesized by dispersion polymerization are excellent candidates for mass cytometry based immunoassays, however they have previously lacked the ability to conjugate biomolecules to the particle surface. We present here three approaches to post-functionalize these particles, enabling the covalent attachment of proteins. Our first approach used partially hydrolyzed poly(N-vinylpyrrolidone) as a dispersion polymerization stabilizer to synthesize particles with high concentration of -COOH groups on the particle surface. In an alternative strategy to provide -COOH functionality to the lanthanide-encoded particles, we employed seeded emulsion polymerization to graft poly(methacrylic acid) (PMAA) chains onto the surface of these particles. However, these two approaches gave little to no improvement in the extent of bioconjugation. In our third approach, seeded emulsion polymerization was subsequently used as a method to grow a functional polymer shell (in this case, poly(glycidyl methacrylate) (PGMA)) onto the surface of these particles, which proved highly successful. The epoxide-rich PGMA shell permitted extensive surface bioconjugation of NeutrAvidin, as probed by an Lu-labeled biotin reporter (ca. 7 × 10(5) binding events per particle with a very low amount of non-specific binding) and analyzed by mass cytometry. It was shown that coupling agents such as EDC were not needed, such was the reactivity of the particle surface. These particles were stable and the addition of a polymeric shell was shown did not affect the narrow lanthanide ion distribution within the particle interior as analyzed by mass cytometry. These particles represent the most promising candidates for the development of a highly multiplexed bioassay based on lanthanide-labeled particles to date. 相似文献
245.
Taha ZA Ajlouni AM Al-Hassan KA Hijazi AK Faiq AB 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,81(1):317-323
Eight new lanthanide metal complexes [LnL(NO(3))(2)]NO(3) {Ln(III) = Nd, Dy, Sm, Pr, Gd, Tb, La and Er, L = bis-(salicyladehyde)-1,3-propylenediimine Schiff base ligand} were prepared. These complexes were characterized by elemental analysis, thermogravimetric analysis (TGA), molar conductivity measurements and spectral studies ((1)H NMR, FT-IR, UV-vis, and luminescence). The Schiff base ligand coordinates to Ln(III) ion in a tetra-dentate manner through the phenolic oxygen and azomethine nitrogen atoms. The coordination number of eight is achieved by involving two bi-dentate nitrate groups in the coordination sphere. Sm, Tb and Dy complexes exhibit the characteristic luminescence emissions of the central metal ions attributed to efficient energy transfer from the ligand to the metal center. Most of the complexes exhibit antibacterial activity against a number of pathogenic bacteria. 相似文献
246.
Hegazy ME El-Beih AA Moustafa AY Hamdy AA Alhammady MA Selim RM Abdel-Rehim M Paré PW 《Natural product communications》2011,6(12):1809-1812
One new cembrane diterpene, 2R,7R,8R-dihydroxydeepoxysarcophine (1), together with three known compounds, 7alpha,8beta-dihydroxydeepoxysarcophine (2), 7beta-acetoxy-8alpha-hydroxydeepoxysarcophine (3), and sarcophine (4), have been isolated from the Red Sea soft coral Sarcophyton glaucum. Their structures were determined using 1D and 2D NMR spectroscopy. 7beta-Acetoxy-8alpha-hydroxydeepoxysarcophine (3) exhibits cytotoxic activity against HepG2, HCT-116, and HeLa cells with IC50 values of 3.6, 2.3, and 6.7 microg/mL, respectively. 相似文献
247.
Abdo A Saeed F Hamza H Ahmed A Salim N 《Journal of computer-aided molecular design》2012,26(3):279-287
Query expansion is the process of reformulating an original query to improve retrieval performance in information retrieval
systems. Relevance feedback is one of the most useful query modification techniques in information retrieval systems. In this
paper, we introduce query expansion into ligand-based virtual screening (LBVS) using the relevance feedback technique. In
this approach, a few high-ranking molecules of unknown activity are filtered from the outputs of a Bayesian inference network
based on a single ligand molecule to form a set of ligand molecules. This set of ligand molecules is used to form a new ligand
molecule. Simulated virtual screening experiments with the MDL Drug Data Report and maximum unbiased validation data sets
show that the use of ligand expansion provides a very simple way of improving the LBVS, especially when the active molecules
being sought have a high degree of structural heterogeneity. However, the effectiveness of the ligand expansion is slightly
less when structurally-homogeneous sets of actives are being sought. 相似文献
248.
El-Khatib AH Esteban-Fernández D Linscheid MW 《Analytical and bioanalytical chemistry》2012,403(8):2255-2267
In this study, single and dual labeling of primary amino and thiol groups of target peptides is presented as a proof of concept. The proposed method allows flexible, independent and sequential labeling of the mentioned residues using lanthanides introduced via DOTA-complexes (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid). The efficiency of the method was optimized using cysteine-containing standard peptides and then applied to bovine serum albumin (BSA) and human serum albumin (HSA) to demonstrate qualitative and quantitative aspects of this strategy. For amino labeling, cysteinyl peptides were immobilized on Sepharose-6B resin and labeled with DOTA-NHS ester followed by metallation with lanthanides. Thiol labeling was carried out using lanthanide-containing metal-coded affinity tags (MeCAT) after elution of peptides from the resin. Complete dual labeling of the standard peptides was demonstrated by liquid chromatography electrospray ionization mass spectrometry, whereas more than 80% of the detected peptides of BSA and HSA were completely dual-labeled. Parallel detection by LC coupled to inductively coupled plasma mass spectrometry (ICP-MS) delivered reliable quantitative information. Thus, the versatile lanthanide choice in both labeling steps allowed estimating primary amino and thiol stoichiometries for the studied samples using different lanthanides. On the other hand, enhancement of ICP-MS signal was achieved as expected when all positions were labeled with the same lanthanide. Finally, linear calibrations of the signal for most of the labeled peptides by standard additions of digested BSA showed a suitable behaviour for quantitative applications and demonstrated the pre-concentration capability of the employed resin. 相似文献
249.
Mohamed Mahmoud Nasef Ezzatollah ShamsaeiPayman Ghassemi Amgad Ahmed AlyAbdul Hamid Yahaya 《Radiation Physics and Chemistry》2012,81(4):437-444
The radiation induced grafting of 4-vinylpyridine (4-VP) onto poly(ethylene-co-tetrafluoroethene) (ETFE) was optimized using the Box-Behnken factorial design available in the response surface method (RSM). The optimized grafting parameters; absorbed dose, monomer concentration, grafting time and reaction temperature were varied in four levels to quantify their effect on the grafting yield (GY). The validity of the statistical model was supported by the small deviation between the predicted (GY=61%) and experimental (GY=57%) values. The optimum conditions for enhancing GY were determined at the following values: monomer concentration of 48 vol%, absorbed dose of 64 kGy, reaction time of 4 h and temperature of 68 °C. A comparison was made between the optimization model developed for the present grafting system and that for grafting of 1-vinylimidazole (1-VIm) onto ETFE to confirm the validly and reliability of the Box-Behnken for the optimization of various radiation induced grafting reactions. Fourier transform infrared (FTIR), thermogravimetric analysis (TGA) and X-ray diffraction (XRD) were used to investigate the properties of the obtained films and provide evidence for grafting. 相似文献
250.
R Hamzah MA Bakar M Khairuddean IA Mohammed R Adnan 《Molecules (Basel, Switzerland)》2012,17(9):10974-10993
A structural study of epoxidized natural rubber (ENR-50) and its cyclic dithiocarbonate derivative was carried out using NMR spectroscopy techniques. The overlapping 1H-NMR signals of ENR-50 at δ 1.56, 1.68-1.70, 2.06, 2.15-2.17 ppm were successfully assigned. In this work, the 13C-NMR chemical shift assignments of ENR-50 were consistent to the previously reported work. A cyclic dithiocarbonate derivative of ENR-50 was synthesized from the reaction of purified ENR-50 with carbon disulfide (CS2), in the presence of 4-dimethylaminopyridine (DMAP) as catalyst at reflux temperature. The cyclic dithiocarbonate formation involved the epoxide ring opening of the ENR-50. This was followed by insertion of the C-S moiety of CS2 at the oxygen attached to the quaternary carbon and methine carbon of epoxidized isoprene unit, respectively. The bands due to the C=S and C-O were clearly observed in the FTIR spectrum while the 1H-NMR spectrum of the derivative revealed the peak attributed to the methylene protons had split. The 13C-NMR spectrum of the derivative further indicates two new carbon peaks arising from the >C=S and quaternary carbon of cyclic dithiocarbonate. All other 1H- and 13C-NMR chemical shifts of the derivative remain unchanged with respect to the ENR-50. 相似文献